JPS5836021B2 - Aminoanthraquinone dye, its manufacturing method and dyeing or printing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to aminoanthraquinone dyes.

According to the present invention, a quaternary ammonium that does not contain a sulfo group and is bonded to a -amino group via a propylene group or a protonated tertiary amino group and a 4-amino group is bonded to a protonated tertiary amino group. Cation type 1,4 containing xylyl group
- A diaminoanthraquinone dye is provided.

That is, the compound provided by the present invention is a compound represented by the following formula (2).

represents a group {in the above formula, R1 and R2 each represent methyl or ethyl, and R3 represents methyl}, and A
e represents an anion, and the methyl group in the xylidino group is 2
and 5 position or 2 and 4 position.

Preferably, the methyl groups in the xylidino group are in the 2 and 4 positions.

Preferably, R and R2 are both methyl.

The nature of the anion A0 is not important as long as it does not adversely affect the dyeing properties of these compounds.

Preferably they are non-chromogenic, suitably anions common in cationic dye technology.

Examples include halogens such as chlorine or bromine, anions such as sulfuric acid, methylsulfate, ethylsulfate, aminosulfonic acid,
perchloric acid, benzenesulfonic acid, toluenesulfonic acid,
Oxalic acid, maleic acid, acetic acid, propionic acid, tartaric acid,
Malic acid, methanesulfonic acid and benzoic acid anions and zinc chloride double salts and boric acid, citric acid, glycolic acid,
Anionic acid of diglycolic acid and adipic acid.

The present invention also provides a method for producing the compound of the above-mentioned formula (1), which comprises: a1) a compound represented by the following formula (1): [In the above formula, Hal represents a halogen]; NR1R2R3 {In the formula, R1, R2 and R3 represent the same thing as defined above} or bi) The following formula ■: [In the above formula, R1 and R2 represent the same thing as defined above] ] A compound represented by formula I is reacted with an agent that dissociates Rρ and Ae to produce a compound in which K■ is a group of the above formula (b), or b11) The following formula ■: ? In the above formula, R represents the same thing as the above definition, R3 represents the same thing as the above definition] A compound represented by the formula R2A {wherein R2 represents the same thing as the above definition,
A represents a group that can be modified to A○} to produce a compound of formula I in which K■ is a group of the above formula (b), or c[) following formula ■: [above In the formula, K■ and Hal are the same as defined above.

Each of the above processes can be carried out in a conventional manner.

Suitably step ai) is carried out in water, an inert organic solvent or a mixture of water and such a solvent.

A suitable reaction temperature is -50 to +250°C, preferably -1
It is 0 to +120°C.

Steps bi) and bii) are suitably carried out under conventional quaternization or protonation reaction conditions, with the quaternization being carried out in an inert solvent, an aqueous suspension or an excess of quaternizing agent. in,
It may be carried out in a buffered medium at elevated temperatures if necessary.

Suitably step c1) is carried out in an inert organic solvent, for example an alcoholic solvent such as butanol, or a mixture of such a solvent with water.

A suitable reaction temperature is 80-150°C, preferably 90-1
The temperature is 10°C.

The reaction is advantageously carried out in the presence of acetate and/or copper salts, such as potassium or ammonium acetate.

If a compound with a particular anion Ae is obtained and it is desired to exchange it for another anion, the interconversion may be carried out in the usual manner, for example using ion exchange techniques.

The resulting compounds can be isolated and purified using conventional methods.

The starting materials used in the above process for producing the compounds according to the present invention are known or can be obtained from available starting materials by conventional methods.

The compounds according to the invention are suitable for substrates containing homo- or mixed polymers of acrylonitrile or asymmetric dicyanoethylene, dyeable with basic dyes, or synthetic polyamides or polyesters modified by the introduction of acid groups, as well as paper and leather substrates. It is useful for dyeing and printing.

Suitably, the polymeric substrates mentioned above are in the form of fibers, filaments or fabrics.

Dyeing or printing can be carried out by conventional methods.

For example, the fiber material can be prepared from a neutral or acidic aqueous medium by
It is dyed at temperatures from 0° C. to the boiling point or even higher temperatures under high pressure.

For leather and paper, for example, German Patent Publication 2306768
No. 1,794,173.

The dyeings obtained on polyacrylonitrile and acid-modified polyamide and polyester substrates cannot be washed, sweated, sublimated,
Shows outstanding fastness to ironing, dry cleaning, over-dying and solvents.

The dye itself shows good water solubility, gives a uniform dyeing, and is hardly affected by iron or salts.

These dyes are dye preparations, e.g. liquid or solid preparations which can be formed in the usual manner, e.g. by comminution or granulation or by dissolving in a solvent, optionally with stabilizers or solubilizers, e.g. urea. It is convenient to use this form.

Such preparations are described, for example, in French patent 157203
No. 0 and No. 1381900.

The following examples serve to further explain the invention.

In the examples, "parts" and "φ" are expressed by weight. Example 1 42.7 parts of 1-(3'-dimethylaminopropino-amino-4-(τ,4''-dimethylphenyl)aminoanthraquinone) were dissolved in 400 parts of chlorobenzene at 60°C, and 14 parts of sulfuric acid Dimethyl was added over 2 hours.

A dye of the following formula was precipitated, which was separated in a furnace at 60°C, washed with chlorobenzene, and then dried under vacuum at 80°C.

This highly water-soluble dye dyes polyacrylonitrile fibers such as Orlon a greenish-blue color.

In addition to good wet fastness, this dye had a marked insensitivity to minerals.

This dye was prepared as a solution in dimethylformamide 6 3
It had a λmax of 0 nm.

Application Example A 20 parts of the dye mentioned in Example 1 and 80 parts of dextrin were ground in a mill for 4 hours.

The same dye mixture was also obtained by pasting with 100 parts of water and then spray drying.

1 part of the preparation thus obtained was made into a paste with 1 part of 40% acetic acid, and the paste was taken up in 200 parts of soft water and briefly boiled.

Diluted with 7000 parts of soft water, added 2 parts of glacial acetic acid and placed in a dyebath at 60° C. with 100 parts of polyacrylonitrile fabric.

This material may, if desired, be pretreated for 10 to 115 minutes at 60 DEG C. in a bath of 8000 parts water and 2 parts glacial acetic acid.

Heat the bath to 98-100°C for 30 minutes, then reduce to boiling temperature
．． After holding for 5 hours, the fabric was taken out and washed with water.

A greenish-blue dyeing with good sunlight and wet fastness properties was obtained.

Alternatively, 10 parts of the dye of Example 1 can be combined with 60 parts of glacial acetic acid and 30 parts of the dye of Example 1.
It was also possible to dye polyacrylonitrile in the manner described above using this dye solution, dissolved in 50% water and having a dye content of approximately 10%.

Application example B 20 parts of the dyestuff of example 1 are mixed with 80 parts of dextrin in a ball mill for 48 hours and 1 part of the resulting preparation is mixed with 40% of 1 part.
A paste was made with acetic acid and the paste was taken up in 200 parts of soft water and briefly boiled.

Using this stock solution, staining was performed as follows.

a) Dilute the stock solution with 7000 parts of soft water and prepare a carrier based on 21 parts of calcined sodium sulfate and 14 parts of ammonium sulfate, 14 parts of formic acid and 15 parts of a reaction product of ethylene oxide and dichlorophenol. was added, and the dyeing solution was placed in a dyebath at 60°C together with 100 parts of acid-modified polyester fabric.

This material may, if desired, be pretreated for 10-15 minutes at 60 DEG C. in a bath of 8000 parts water and 2 parts glacial acetic acid.

The temperature of this bath was raised to 98-100° C. over 30 minutes, kept at boiling temperature for 1 hour, and the fabric was taken out and washed with water.

A uniform greenish-blue dyeing with good wet fastness properties was obtained.

b) The stock solution is diluted with 3000 parts of soft water, 18 parts of calcined sodium sulfate and 6 parts of ammonium sulfate and 6 parts of formic acid are added, and the staining solution is incubated at 60°C with 100 parts of formic acid.
It was placed in a dye bath together with the acid-modified polyester fabric.

The bath was closed, heated to 110° C. in 45 minutes, kept at this temperature for 1 hour under shaking, then cooled to 60° C. in 25 minutes, and the dyeing was removed and washed with water.

A uniform greenish-blue dyeing with good wet fastness properties was obtained.

C) The same operation as b) above was repeated, but the closed container was heated at 120° C. for 1 hour.

Application example C A stock solution was prepared in the same manner as in Application Example B above.

This solution was diluted with 7000 parts of soft water, and 21 parts of calcined sodium sulfate and 14 parts of ammonium sulfate were added.
Add 14 parts of formic acid and 15 parts of a carrier based on the reaction product of ethylene oxide and dichlorophenol, buffer this solution to pH 6 using an acid buffer solution, and add 100 parts of acid-modified polyamide fabric. It was placed in a dye bath at a bath ratio of 1=80.

The bath was heated to 98°C in 45 minutes, boiled for 1 hour, and the fabric was removed and washed with running water at 70-80°C and then with cold water.

The fabric was then dried and ironed.

Example 2 A greenish-blue dyeing with good fastness properties was obtained. 42.7 parts of 1-(3'-dimethylaminopropino-4(2'/, ,i//-dimethyl7enyl) ) Aminoanthraquinone was dissolved in 400 parts of toluene at 80°C.

11 parts of hydrogen chloride was introduced into the mixture under stirring over 3 hours, and the protonated product was precipitated.

This was oven separated at 60°C, washed with 200 parts of toluene, and vacuum dried at 80'C.

Example 3 4168 parts of 4-(3"-chloroprobyl)amino 1-
(2',4'-dimethylphenyl)aminoanthraquinone in 400 parts of pyridine at 100-110°C.
Stirred for 8 hours until the chromatogram showed only trace amounts of initial material testing the reaction mixture.

The resulting crystal aggregate was diluted with 200 parts of chlorobenzene and then furnaced at 60°C.

After washing with chlorobenzene until the effluent becomes colorless,
This dye was vacuum dried at 100°C.

4-(I-chloroprobyl)amino-1-(2',4
'-dimethylphenyl)aminoanthraquinone is 4-
(f-hydroxyprobyl)amino-1-(2/,
4/-dimethylphenyl)aminoanthraquinone,
It was obtained by reacting with thionyl chloride in chlorobenzene at 60-70°C.

Example 4 50.2 parts of N-3-(4'-bromoanthraquinonyl-17-amino)probylpyridinium bromide in 200 parts of 1-amino-2,5-dimethylbenzene.
Stirred at 00'C for 8-10 hours while adding 19 parts anhydrous potassium acetate and 1 part copper sulfate.

The color of the reaction medium changed from red to violet and then blue and condensation took place.

When the chromatogram shows that the condensation is complete, the reaction product is diluted with 100 parts of 1,2-dichlorobenzene and
The precipitated dye was isolated by filtration at 60°C.

The residue was washed with 1,2-dichlorobenzene and heated to 1oooC.
It was vacuum dried.

The residue may be further purified by recrystallization from n-butanol after washing and before drying.

This dye is available as a solution in dimethylformamide at 627
It had a λmax of μm.

The starting material is brominated 1-(3'-bromopropyl)aminoanthraquinone, for example in an aqueous hydrochloric acid suspension;
This product was then reacted with pyridine in a known manner.

Examples 5 to 8 could be produced in the same manner as in the previous examples.
Other dyes of formula I are shown in the table below.

The dyes of Examples 2 to 8 give greenish-blue dyeings to polyacrylonitrile, such as "Orlon", and to acid-modified polyester and nylon fabrics.

Claims (1)

[Claims] 1 General formula ■: {In the above formula, R1 and R2 each represent methyl or ethyl, R3 represents methyl}, and A
e represents an anion, and the methyl group in the xylidino group is 2
and the 5-position or the 2- and 4-position]. 2. The compound according to claim 1, wherein the methyl groups in the xylidino group are at the 2 and 4 positions in the general formula (2), and % is a group in which R1 and R2 are both methyl in the formula (b). 3. The compound according to claim 1, wherein the methyl groups are at the 2 and 4 positions in the general formula (1), and K (2) is a group of formula (a). 4. The compound according to claim 1, wherein in the general formula (2), the methyl groups are at the 2 and 4 positions, and K (2) is a group in which R1 and R2 are both ethyl in the formula (b). 5. The compound according to claim 2, wherein Ae in general formula I is a methyl sulfate anion. 6. The compound according to claim 3, wherein Ae in the general formula (2) is a methyl sulfate anion. 7. The compound according to claim 4, wherein Ae in General 2〇 is a methyl sulfate anion. 8 General formula I: {In the above formula, R and R2 each represent methyl or ethyl, R3 represents methyl}, and A
e represents an anion, and the methyl group in the xylidino group is 2
and 5-position or 2- and 4-position] When producing a compound represented by ai) the following formula ■: [In the above formula, Hal represents a halogen] A compound represented by pyridine or 2NR1R2R3{ [In the above formula, R1, R2 and R3 are the same as defined above] or bi) the following formula ■: [In the above formula, R1 and R2 are the same as defined above] The compound shown is reacted with an agent that dissociates R3■ and Ae to produce a compound of formula (2) in which % is a group of the formula (b), or b11) the following formula (2):. [In the above formula, R1 represents the same thing as the above definition, R3 represents the same thing as the above definition] A compound represented by the formula R2A {wherein R2 represents the same thing as the above definition,
A represents a group capable of Ae modification} to produce a compound in which K■ in formula 1 is a group of the formula (b), or ci) the following formula ■: [in the above formula, K■ and Hal are the same as defined above.] A method comprising reacting a compound represented by the following with xylidine. 9 General formula I: represents ethyl, R3 represents methyl, A○ represents an anion, and the methyl groups in the xylidino group are at the 2 and 5 positions or the 2 and 4 positions] Aminoanthraquinone dye represented by.